Filter Material for Generating Oxygen and/or Hydrogen From A Source

ABSTRACT

A filter material for generating oxygen and/or hydrogen gas from a source having a porous boron doped carbon film with diRuthenium/diRuthenium molecules in direct contact with the porous boron doped carbon film, a synthetic film having at least one zeolite crystalline body in direct contact with the nanocarbon tubules, or both in a continuous alternating arrangement.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of co-pending application Ser.No. 12/459,706 filed Jul. 7, 2009, now allowed, which claimed priorityto U.S. Pat. No. 7,579,103 that issued on Aug. 25, 2008 and claimedbenefit to U.S. Provisional Application Ser. No. 60/967,756 filed Sep.7, 2007, to which the present application claims priority to both theapplications and issued patent are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to a filter material for the oxidation ofwater and/or exhaled air to bimolecular oxygen and/or hydrogen gas. Inparticular, a filter material containing at least onediRuthenium/diRuthenium complex affixed to a Boron doped carbon film anda synthetic film containing zeolite crystalline. The filter material ofthe present invention provides not only a high separation efficiency dueto the use of the diRuthenium/diRuthenium complex, but also providesadditional separation efficiency by coupling the catalyst properties ofthe diRuthenium/diRuthenium complex with the adsorption high separationefficiency of the zeolite with embedded nanocarbon tubules.

BACKGROUND OF THE INVENTION

Historically Oxygen generation has been achieved by electrolysis ofwater, photolysis and chemical conversions. One method still in usetoday is the Pressure Swing Adsorption Cycles (“PSA”) as described inU.S. Pat. No.: 2,944,627 which is herein incorporated by reference. In aPSA system oxygen is produced by the selective adsorption of nitrogenfrom a feed air stream. The PSA has at least one, often two adsorbentbeds, which are designed to attract oxygen gases at low pressures andrelease the adsorbed oxygen at higher pressures. The PSA processes canbe used to separate gases in a mixture because certain gases tend to beattracted to different solid surfaces more or less strongly than others.

Another Oxygen generation process that uses some of the principals ofthe PSA process is called the Vacuum Swing Adsorption (VSA). In a “VSA”process, gases are separated using pressure but unlike the PSA processit is done at lower absolute pressures. Although these methods do work,they require multiple pressurized vessels and valve systems makingportability difficult if not impossible. That is, these systems requirevalve operations either done automatically or by carefully calculatedtiming cycles controlled by a PLC. Accordingly, these systems are quitelarge and therefore prevent a patient from directly wearingoxygen-generating system as a portable system.

Over the years, improvements to the PSA and VSA systems were made suchas in U.S. Pat. No.: 3,313,091 incorporated herein by reference. Whilethe earlier PSA and VSA systems used crossover valving and Zeoliteadsorbing material to produce a product high in Oxygen purity, thesesystems were neither consistent nor simple. To maintain consistentoxygen product, U.S. Pat. No. 3,313,091 used a vacuum pump to draw partof the adsorbed termed “waste gases” from the vessel or bed beingpurged. These advancements over the earlier PSA and VSA systems however,required more complex electromechanical design additions including addedphase controlling, e.g. gas entry, vacuuming re-pressurization anddumping to allow Oxygen gas as a product of several cycles to transferthrough and out to a user or patient did provide a higher yield. Nor didit compensate for the problems of associated with nitrogen loading tooxygen ratios, or electrostatic charge build up on the zeolite surface,clogging and preventing transfers and fouling.

The next advancement in oxygen filtration came in 1980 and was describedin U.S. Pat. No. 4,222,750, which is herein incorporated by reference.In this patent the vessels or beds of adsorbing filtration materialscyclically underwent both periods of adsorption in which said vessel orbed received gas from a compressor then reabsorbed from the beds using avacuum pump. As one can see, this improvement added even more equipmentto the systems making it even less likely to be used as a portablesystem.

Therefore, what are needed are filters that can be used withoutelectrostatic charge build up, nitrogen loading to oxygen adsorptionratios plugging, and that eliminate expensive and bulky pressurizedchambers/valves and other large equipment that can generate sufficientamounts of oxygen to be used in a portable breathing device. That is afiler material that can be produce oxygen at a rate and concentrationnecessary to maintain breathing is a patient without pressurizing anddepressurizing chambers and opening and closely complex valve systems.The present invention provides a filter material that overcomes theshort comings of the prior art and can be used in a truly portableoxygen generating system capable of maintaining proper oxygen levelsnecessary for breathing by a patient. The present invention is discussedin the section below.

SUMMARY OF THE INVENTION

The present invention is directed to filter material that does notrequire pressurized chambers to operate. In particular, the presentinvention is directed to a filter material for removing oxygen and/orhydrogen gas from water and/or exhaled air comprising a porous borondoped carbon film comprising diRuthenium/diRuthenium molecules and atleast one type of electronegative ion in direct contact with the porousboron doped carbon film whereby oxygen and/or hydrogen gas is generatedfrom a source as it passes across said filter material.

In one embodiment of the present invention, one diRuthenium molecule ofeach the diRuthenium/diRuthenium molecules of the doped Boron carbonfilm has the following formula [Ru₂(CO)₄(u-n²⁻O₂CR)₂L₂]_(x) wherein u isa bridging ligand selected from the group consisting of [Ru₂(EDTA)₂]²⁻,(CO)₄, F⁻, Co₃ ⁻², NO⁺ (Cationic), Hydrogen-bonded aromatic/carboxylicAcid—(either for multiple attachments as polymerization or singular, atthe double bonded Oxygen or sites within), ethylenediamine, halides asanionic ligands, carboxylic acid, unsaturated hydrocarbons, Nitric Acidcoordinating to a metal center either linear or bent, butadiene,carboxylate ligands, anionic (RO— and RCO₂ ⁻² (wherein R is H or alkylgroup) or neutral ligands (R₂, R₂S, CO, CN⁻), CH₃CN (Acetonitrile), NH₃(Ammonia ammine) F⁻, Cl⁻, tris(pyrazolyl)borates, Scorpionate Ligand” aboron bound to three pyrazoles; the “pincers” of the compound refer tothe nitrogen hetero atoms from two of the pyrazole groups (C₃H₄N₂) whichcan bind a metal) and mixtures thereof, preferably [Ru₂(EDTA)₂]²⁻;

wherein n is at least 2 and depends on the denticity of themolecule—(that is, the number of donor groups from a given ligandattached to the same central atom); wherein L is a ligand selected fromthe group consisting of [Ru₂(Ph₂PCH₂CH₂PPh₂)(EDTA)]²⁺, C₆H₆, R₂C=CR₂(wherein R is H or an alkyl), 1,1-Bisdiphenylphosphino methane,diethylenetriamine [diene] bonds preferably tridentate,triazacyclononane [diene] bonds preferably tridentate,triphenylphosphine and mixtures thereof;wherein CR is carboxylic acid, carboxylate ligands, anionic (RO— andRCO₂ ⁻ (wherein R is an alkyl group)) or neutral ligands (R₂, R₂S, CO⁻,CN⁻ (wherein R is an alkyl group)) and mixtures thereof; and x is about1 to about 30, preferably 1 to about 20 and more preferably 1 to about10.

The other diRuthenium molecule of each the diRuthenium/diRutheniummolecules of the doped Boron carbon film is attached to adiRuthenium-substituted polyoxometalate as an electrochemical catalysthaving the following formula [WZnRu^(III) ₂ (OH)(H₂O)(ZnW₉O₃₄)₂]⁻¹⁴. Inaddition to these features, the porous boron doped carbon film mayfurther comprise an embedded nanocarbon tubular mesh network.

Since Ruthenium ions can have adverse effects on a patient should theions become free from the filter, the filter material of the presentinvention may further comprise a Ruthenium ion capturing siderophore.The siderophore can be connected to the opposite surface of the porousboron doped carbon film in which the diRuthenium/diRuthenium moleculesare attached. The siderophore can be in the form of a plate orstructured as a hollow tub made from a light metallic alloy, aluminumcopper oxide as example, the hollow tube is impregnated polysulfateresin, EDTA or mixture thereof. The hollow tube can have a plurality ofpores dispersed throughout so as to aid in the capturing of freeionically charged ions. In particular, the siderophore can be charged soas to capture any free ruthenium ions that may become dislodged from theporous boron doped carbon film before they enter into a patient.

The filter material may also comprise a thin synthetic film with carbonnanotubles attached to the film and zeolite crystalline bodies in directcontact with the nanocarbon tubules. Zeolites typically are hydratedaluminosilicate minerals having micro-porous structures. Accordingly,the synthetic zeolite synthetic film of the present invention operatesas a molecular sieve where the maximum size of the molecular or ionicspecies that can enter the pores of a zeolite is controlled by thediameters of the tunnels in the sieve that are conventionally defined bythe ring size of the aperture. For example, a zeolite complex having an8-ring structure is a closed loop built from 8 tetrahedrally coordinatedsilicon (or aluminum) atoms and 8 oxygen atoms and itself comprises amultiplicity of pores. In other words, the size of the apertures in thezeolite synthetic film that controls entry of the particular ions intothe internal pore volume of the zeolite synthetic film and is determinedby the number of T atoms (T=Si or Al) and Oxygen in the ring. Theapertures are classified as ultra large (>12 membered ring) (large 12),medium (10) or small (8). Aperture sizes range form about 0.4 nm for an8 ring structure such as zeolite A, about 0.54 nm for a 10 ringstructure such as ZSM-5 and about 7.4 nm for a 12 ring structure such aszeolite X and ZSM-12, all of which can used in the present invention.

The synthetic film itself comprises a multiplicity of pores having adiameter of about 0.1 to about 3.0 nm providing an Oxygen sieving effect(0₂=2.96 A° and N₂=3.16 A° ). The zeolite crystalline bodies attached tothe nanocarbon tubules overlap at least part of the pores. The porousboron doped carbon film comprising diRuthenium/diRuthenium moleculestogether with the thin synthetic film having carbon nanotubles attachedand zeolite crystalline bodies in direct contact with the nanocarbontubules form a repeating unit that can be used to make up a filter thatcan be used to remove oxygen and/or hydrogen gas from a supply source.

Additional embodiments and details of the present invention are providedin the figures and the Detailed Description section below.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows a prospective view of the front surface of the porous borondoped carbon film comprising diRuthenium/diRuthenium molecules of thefilter material of the present invention.

FIG. 2 shows a prospective view of the back surface of the porous borondoped carbon film comprising diRuthenium/diRuthenium molecules andsiderophore plate of the filter material of the present invention.

FIG. 3 shows a cross-sectional view of the surface of the synthetic filmcomprising zeolite crystalline bodies of the filter material of thepresent invention.

FIG. 4 shows a cross sectional view of a plurality of alternatingscreens of the filter material of the present invention.

FIG. 5 shows a prospective view of a plurality of alternating screens ofthe filter material of the present invention in a filter cartridge.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to high Oxygen generating filtermaterial comprising two different catalytic screens in alternatingorientation. The DiRuthneium/diRuthneium screen functioning as anelectrocatalyst generating Oxygen, the other a Zeolite an adsorptionscreen. Together and both types of screens having embedded nanocarbontubular mesh networks allow for greater Oxygen production and at muchhigher flow rates achievable than prior art. In the prior PSA and VSAsystems rapid breathing patients and or higher flow rates above 5 LPMdisplayed a diminishing Oxygen concentration leaving the apparatus,typically liter flows exiting such prior art systems above 6.5 LPMshowed measured 4-8% diminution in Oxygen concentrations generated, theinvention achieves liter flows of 8-12 LPM with little to no Oxygenconcentration effects, less than 1-2% diminution.

The alternating orientation is specifically designed to prevent both thebuild up of radical intermediates during Oxygen generation that causedecomposition of the Oxygen generating filter and build up of excesswater on the filter material. As well as a design incorporating the useof electrostatic charge build up removal and venting of surface filterconstituents not adsorbed that prior art does not have, certainly cannotachieve in portability.

The first screen of the alternating filter material is a porous borondoped carbon film comprising diRuthenium/diRuthenium molecules and atleast one type of electronegative ion directly attached to the carbonfilm. The second screen arranged behind the first screen is made out ofa synthetic film comprising at least one zeolite crystalline body indirect contact with concentrically arranged nanocarbon tubules attachedto the synthetic film. The synthetic film comprises a multiplicity ofpores having a diameter of about 0.1 nm to about 3.0 nm. The zeolitecrystalline bodies are attached to the nanocarbon tubules and overlap atleast a portion of the pores. It is this structure that makes up asingle repeatable unit and can be placed in series to generate higheroutputs of Oxygen from a given source.

The synthetic film comprises a multiplicity of pores having a diameterof about 0.1 to about 3.0 nm. The zeolite crystalline bodies areattached to the nanocarbon tubules and overlap at least a portion of thepores. It is this structure that makes up a single repeatable unit andcan be placed in series to generate high Oxygen output form water vapor,water vapor from exhaled air or another source.

The unique diRuthenium/diRuthenium molecule used in the first screencontains several Ruthenium atoms. Chemically “Ruthenium” is generallyfound in ores with the other platinum group metals in the Ural Mountainsand in North and South America. Small but commercially importantquantities are also found in pentlandite extracted from Sudbury, Ontarioand in pyroxenite deposits in South Africa. Commercially Ruthenium isisolated through a complex chemical process in which hydrogen is used toreduce ammonium ruthenium chloride yielding a powder. The powder is thenconsolidated by powder metallurgy techniques. Historically, Rutheniumwas realized out of residues that were left after dissolving crudeplatinum. Ruthenium is a transition metal and as with most transitionmetals are excellent Lewis acids. That is they readily accept electronsfrom many molecules or ions that act as Lewis bases. When a Lewis basedonates its electron pair to a Lewis acid, it is said to coordinate tothe Lewis acid and form a coordinate covalent bond. When Lewis basescoordinate to metals acting as Lewis acids and form an integralstructural unit, a coordination compound is formed. In this type ofcompound, or complex, the Lewis bases are called ligands and suchligands may be cationic, anionic or charge neutral.

Another portion of the Ruthenium complex of the present invention is aPolyoxometalates or “POM.” As a class, POMs are very functional for useas catalysts and are able to activate molecular Oxygen and/or Hydrogenperoxide as reagents in oxidation reactions. However, one of the majorproblems with using Ruthenium containing molecules as catalyst is thedegeneration of the Ruthenium catalyst and the danger of Rutheniumpoisoning to those in contact with its ions which may becomedislodged/decomposed off its bound couple. The design of the filtermaterial of the present invention overcomes these problems in part byusing a uniquely designed siderophore.

The first screen of the filter material of the present inventioncomprises a boron doped synthetic carbon thin film and a charged platebonded to the opposite side of the synthetic carbon film than theRuthenium complex. Both the boron doped synthetic carbon thin film andthe charged plate function synergistically as siderophores. Asiderophore is a compound that will attract and bond free charged ions.In other words, a complex that will capture freely charged ions beforethe ions continue through the filter materials and out of the filter andinto the airflow of a person. The siderophores of the present inventionare negatively charged so as to be specific for positive charged ionsincluding Ruthenium ions. Thus, capturing any positive Ruthenium ionsthat may become dislodged from the diRuthenium/diRuthenium complex ofthe present invention overcomes the shortcomings of using Ruthenium as acatalyst for generating Oxygen and therefore provides a safeguardagainst Ruthenium poisoning.

One embodiment of the present provides a filter material for removingoxygen and/or hydrogen gas from a source comprising a porous boron dopedcarbon film having diRuthenium/diRuthenium molecules and at least onetype of electronegative ion attached either directly to the carbon filmor, optionally, via an intermediate compound and/or structure. Whetherthe diRuthenium/diRuthenium molecules of the present invention that arein direct contact with porous boron doped carbon film or are attachedvia an intermediate compound and/or structure, they are ionicallybonded.

In one embodiment of the present invention, one diRuthenium molecule ofeach of the diRuthenium/diRuthenium molecules of the present inventionhas the following formula (I) [Ru₂(CO)₄(u-n²⁻O₂CR)₂L₂]_(x) wherein u isa bridging ligand selected from the group consisting of [Ru₂(EDTA)₂]²⁻,(CO)₄, F⁻, Co₃ ⁻², NO⁺ (Cationic), Hydrogen-bonded aromatic/carboxylicAcid—(either for multiple attachments as polymerization or singular, atthe double bonded Oxygen or sites within), ethylenediamine, halides asanionic ligands, carboxylic acid, unsaturated hydrocarbons, Nitric Acidcoordinating to a metal center either linear or bent, butadiene,carboxylate ligands, anionic (RO— and RCO₂ ⁻² (wherein R is H or alkylgroup) or neutral ligands (R₂, R₂S, CO, CN⁻), CH₃CN (Acetonitrile), NH₃(Ammonia ammine) F⁻, Cl⁻, tris(pyrazolyl)borates, Scorpionate Ligand” aboron bound to three pyrazoles; the “pincers” of the compound refer tothe nitrogen hetero atoms from two of the pyrazole groups (C₃H₄N₂) whichcan bind a metal) and mixtures thereof, preferably [Ru₂(EDTA)₂]²⁻;

wherein n is at least 2 and depends on the denticity of themolecule—(that is, the number of donor groups from a given ligandattached to the same central atom); wherein L is a ligand selected fromthe group consisting of [Ru₂(Ph₂PCH₂CH₂PPh₂)(EDTA)]²⁺, C₆H₆, R₂C=CR₂(wherein R is H or an alkyl), 1,1-Bisdiphenylphosphino methane,diethylenetriamine [diene] bonds preferably tridentate,triazacyclononane [diene] bonds preferably tridentate,triphenylphosphine and mixtures thereof;wherein CR is carboxylic acid, carboxylate ligands, anionic (RO— andRCO₂ ⁻ (wherein R is an alkyl group)) or neutral ligands (R₂,R₂S, CO⁻,CN⁻ (wherein R is an alkyl group)) and mixtures thereof; ; and x isabout 1 to about 30, preferably 1 to about 20 and more preferably 1 toabout 10.

The other molecule of each of the diRuthenium/diRuthenium molecules ofthe present invention is a diRuthenium-substituted polyoxometalatehaving the following formula (II) Na₁₄[Ru₂Zn₂(H₂O)₂(ZnW₉O₃₄)₂]substituted to WZnRu^(III) ₂ (OH)(H₂O)(ZnW₉O₃₄)₂]⁻¹⁴. The distancebetween each Ruthenium in the diRuthenium molecule is about 2.0angstroms to about 3.18 angstroms, preferably about 2.25 angstroms toabout 3.0, and more preferably about 2.50 angstroms to about 2.80angstroms.

For example, the Ru-Ru distance of 3.18 Å of theNa₁₄[Ru₂Zn₂(H₂O)₂(ZnW₉O₃₄)₂] substituted to WZnRu^(III) ₂(OH)(H₂O)(ZnW₉O₃₄)₂]⁻¹⁴ as an electrocatalyst POM disclosed in U.S. Pat.No. 7,208,244 limits the amount of oxygen that may be generated. Also,because the POM structure as used in the prior art is subject to torsionand rotation upon impact by water molecules, the consistency of oxygengeneration is necessarily limited in a system involving water flowing ateven modest rates. Accordingly, neither di-ruthenium POMs nordi-ruthenium sawhorse molecules have heretofore been used for thegeneration of breathable oxygen.

In one particular embodiment of the present invention, thedi-ruthenium-substituted polyoxometalates described in U.S. Pat. No.7,208,244 to Shannon et al., the entirety of which is hereinincorporated by reference, can be used to in connection with the borondoped carbon thin film as described above so as to provide the benefitsinventive filter material.

In yet another embodiment of the present invention, the filter materialfurther comprises a Ruthenium ion capturing siderophore plate connectedto the opposite surface of the carbon film in which thediRuthenium/diRuthenium molecule is attached. The siderophore plate isionically charged so as capture free Ruthenium ions that becomedislodged from said porous boron doped carbon film. The siderophoreplate can be selected from the group consisting of negative or positivecharged ions, in particularly resin clay in which the clay is moldedinto a hollow tubular plate having a plurality of pores. In particular,the siderophore can be polysulfinate impregnated resin ,ethylenediaminetetraacetic acid (EDTA) containing and mixtures thereof.In one particular embodiment of the invention the siderophore plate isattached to one end of the nanotubules of the carbon doped film and atleast a portion of the siderophore plate is directly attached and/orembedded into the thin film. This design allows the siderophore plate tobe capable of capturing and ionically bonding free Ruthenium ions.

As discussed above, this is essential when the filter material havingRuthenium atoms is used to produce Oxygen for breathing. In anembodiment wherein Oxygen produced by the filter material is not usedfor breathing but is used instead for an industrial process, thesiderophore plate is less important.

In yet another embodiment of the present invention, the porous borondoped carbon film can further comprises a nanocarbon tubular meshnetwork. The nanotubles of the nanocarbon tubular mesh network have adiameter of about 20 nanometers to about 450 nanometers, preferable 20nanometers to about 250 nanometers and more preferably about 20nanometers to about 100 nanometers. The nanocarbon tubular mesh networkis designed so that each tubule can carry large currents in a relativelylow resistance flow, which is used to destabilize the oxygen-hydrogenbonds in water so as to make them easier to split the bonds in order toproduce bimolecular Oxygen and/or hydrogen. According, the energy andthe time necessary to split the bonds is less, thus making it quickerand easier to produce bimolecular Oxygen. The nanotubule network extendsabove the supporting POM matrix by about 0.2 to about 5.0 microns.

Attaching the diRuthenium to the carbon thin film begins with theattachment of the Carbon to a substrate. In one embodiment of thepresent invention a silicon substrate, or like, is used to allow thecarbon atoms from Chemical Vapor Deposition (CDV) to nucleate on thesubstrate surface initiating the tetrahedral coordinated Sp3 orbitalnetwork. The CDV are hydrogen and methane as precursor gases which usingthe “heated methodology”. The heated methodology, for example, can use afilament to provide the diffusion of the reactive species mostly “methylradical” to interact with the substrate surface and allow the carbonatoms to be absorbed by the surface and growth coalescence to occur.Once complete the thin-filmed surface is believed to be primarilytertiary carbon atoms with single C—H bonds.

The doping of the carbon thin film may be completed using boron,fluorine and/or nitrogen. With increased concentrations of the dopinglevel, the insulator behavior of the diamond (carbon) alters to one of asemiconductor and further to a full metallic behavior. In order toachieve this electrochemistry effect, the level of boron doping has tobe sufficient to cause a low ohmic drop in the diamond (carbon) level,but not so low as to alter or disturb the crystalline structure inducinga graphite phase during the doping synthesis. One way this can beachieved is to do the doping with Fluorine as a compounded vapor, whereupon contact with the carbon thin film, the Fluorine interacts with boththe hydrogen and boron forming a bond as the ion. Another possible wayto achieve this is doping the carbon with a mixture of both boron andfluorine. As fluorine is a case of negative doping i.e., the negative Fatom has an extra electron and a slightly lower energy level. (i.e.about 0.028-0.32 eV as opposed to Boron at about 0.35 eV). Typically,the carbon-fluoride bond is covalent and very stable, as can be seen inseveral common fluorocarbon polymers, such as, poly(tetrafluoroethene)and Teflon. In the alternative, the invention may utilize the depositionof graphite onto the substrate to produce nanotubules by micromechanicalcleavage of high quality graphite.

Still yet another alternative is to vapourize the Boron Oxide and lowvolume- molar Hydroflourine (less than about 0.22 litters to about 0.34liters per about 1.9 liters to about 2.5 liters methane). As discussedabove, fluorine containing compounds such as, perfluoroalkyl-alkoxysilanes and/or trifluoropropyl-trimethoxysilane (TFPTMOS), can be usedto interact with the carbon boron doped thin film providing that thefluorine containing compound has at least one carbon-metal bond permolecule. The —CF₃ and —OCF₃ moieties provide further variation, andmore recently the —SF₅ group. An Additional alternative in utilizing theboron doped with the fluorine atoms as BF₃.

Still yet another alternative is the vaporizing the Boron Oxide andHydrofluroine gas to interact with the methane and using fluorinecontaining compounds, as pointed out above, such asperfluoroalkyl-alkoxy silanes, with trifluoropropyl-trimethoxysilane(TFPTMOS) being preferred. A necessary requirement is that the fluorinecontaining compound has at least one carbon-metal bond per molecule.)

The thin film functions now as a Semiconductor as in this case of ourshell composed of the boron doped synthetic diamond (carbon) thin film,which is also used as anchor, and the bonding to keep the alignment ofthe Ruthenium complexes in the sawhorse orientation and as well as POMfrom excessively separating and twisting when flows greater than 20liters/min and/or water flows of greater than 4 liters/25 seconds arepassed across the filter material of the present invention. Therefore,not only does the boron doped carbon thin film provide semiconductorproperties, but it also functions to prevent the diruthenium moleculesfrom becoming distorted under high flows. In addition, the boron dopedcarbon thin film together with the fluorine causes an inductive effectthat amplifies the electronegative moiety bonded to the sawhorseorientated Ruthenium complex as well as both inner sphere ligands whileequally extending out to the Diruthenium-POM as outer sphere bonding.

The carbon in the diamond or graphite structure is sp³ hybridized whilethe Boron (non carbon, i.e., non-diamond) is sp² species. The specifichybridization states of the carbon and Boron discussed above areimportant in providing electrical conductance to the thin film so thatthe thin film functions as both an anchoring substrate and an Oxygengenerating electrode. In order to be effective for the stated purposeabove, the thin film must be boron doped in a range between about 2100ppm to about 6,800 ppm/0.1 cm of thin film (screen) size.

In yet another embodiment of the present invention, the filter materialof the present invention further comprises a synthetic film comprising aplurality of nanocarbon tubules attached and/or embedded thereon to forma nanocarbon tubule mesh network. The synthetic film of the presentinvention is selected from the group consisting of SiO₄, AlO₄, andmixtures thereof. The crystal structure is based upon repeating unitsconsisting of a silicon atom (+4 valence) surrounded by four oxygenatoms (−2 valence) in a tetrahedral configuration. Two Si atoms, givingthe tetrahedral net valence of zero, share an oxygen molecule. Whenaluminum (with a valence of +3) is substituted in the tetrahedralorientation a net charge −1 occurs and thus gives rise to the cationexchange properties of zeolites (further discussed below). The syntheticfilm being positioned in close communication with the surface of theporous boron doped carbon film in which the siderophore is attached. Thesynthetic film of the present invention further comprising at least onezeolite crystalline body that is in direct contact with the nanocarbontubule mesh network attached and/or embedded thereon. The synthetic filmhas a multiplicity of pores with a diameter of about 0.1 to about 3.0nm, preferably about 0.1 nm to about 3.4 nm and more preferably about toabout 2.0nm to about 2.9 nm.

In one embodiment of the present invention, the zeolite crystallinebodies are directly attached to the nanocarbon tubules of the nanocarbontubule mesh network so that the zeolite crystalline bodies overlap atleast part of the pores in the synthetic film. This configuration allowsOxygen and/or Hydrogen generated from the reaction of water moleculeswith the zeolite/nanotubles to flow through the pores of the syntheticfilm to be collected and used for a given purpose. It is the combinationof the diRuthenium/diRuthenium containing porous boron doped carbon filmand the synthetic film containing zeolite crystalline bodies attached tothe nanocarbon tubule mesh network overlapping at least part of thepores in the synthetic film that forms a repeating unit of the filtermaterial of the present invention.

Zeolites used in the present invention have a crystal structureconstructed from a TO₄ tetrahedral configuration, where T is either Sior Al. In addition to a large number of naturally occurring zeolitesthere is a wide range of synthetic zeolites as well. The crystalstructure of zeolites is based upon repeating units consisting of asilicon atom (+4 valence) surrounded by four oxygen atoms (−2 valence)in a tetrahedral configuration. Each oxygen atom is shared by two Siatoms, giving the zeolite is a tetrahedral structure and a net charge ofzero. When aluminum (with a valence of +3) is substituted in thetetrahedral configuration the zeolite will have a net charge of −1. Thisnegative charge gives rise to the cation exchange properties ofzeolites. Zeolites also have very uniform defined pore sizes as well ashigh porosity, which occur as a consequence of their unique crystalstructures. For this reason, zeolites are useful as molecular sieves.

However, un-split water frequently blocks the pores of certain zeolitesand therefore often these zeolites often become fouled and loss theirseparation qualities. The structure of the filter material of thepresent invention allows the zeolites attached to the tubular meshnetwork to remain “unclogged” and functional for a longer period of timebecause the nanotubles of the filter material destabilizes thehydrogen/oxygen bond in water thereby making it easier for thediruthenium molecules of the filter material to split water into oxygenand hydrogen. The more water that is split by the diruthenium molecules,the higher the oxygen/hydrogen generation and the less water availableto clog the pores of the zeolite attached to the nanotubules of thesynthetic film of the present invention. Once the oxygen and/or hydrogenare generated it can be captured and used for breathing, storage orindustrial uses.

The pore size of the zeolites used is also critical. If the pres are toolarge water can pass through the zeolite filter and not be split tooxygen and hydrogen, too small the oxygen and/or hydrogen produced canbe retained and not passed out of the filter so that they can beutilized. Therefore, it is important that it is possible to fine-tunethe pore opening of zeolites so as to allow the adsorption of specificmolecules while excluding others based on size. One method to change thepore size of the zeolite is to change the exchangeable cation from onecation to another. For example, when Na+ ions are replaced by Ca++ ionsin zeolite A, the effective aperture size increases. This can also beaccomplished by changing the Al/Si ratio in the zeolite. An increase inthe ratio of Si to Al will slightly decrease the unit cell size,decrease the number of exchangeable cations, thus freeing the channelsand make the zeolite more hydrophobic in character.

Zeolite used in the present invention are mainly composed ofalumin-silicates wherein the alumina substrate contains alumina poresthat function as molecular sieves that allow some atoms but excludesothers so as to purify a chosen end product. For purpose of thisapplication the term “molecular sieve” refers to a particular propertyof these materials, i.e. the ability to selectively sort molecules basedprimarily on a size exclusion process. The zeolites that can be used inthe present invention include any one of a family of hydrous aluminumsilicate minerals, typically of alkali metals and alkaline earth metalswhose molecules enclose cations of sodium, potassium, calcium,strontium, or barium, or a corresponding synthetic compound.

Accordingly, the filter material of the present invention is constructedfrom the repeating unit comprising the boron carbon doped filmcontaining diRuthenium molecules on one side of the film and ansiderophore to capture free Ruthenium ions on the other, followed by asynthetic film containing a carbon nanotubular mesh network attached tosynthetic film and the zeolite crystalline bodies. Several of theserepeating units can be amassed in series so as to provide a filtermaterial for high output Oxygen and/or Hydrogen generation. This uniquefilter material combines two different materials, which results in a newmaterial having characteristics that are different than those of thebasic materials. As such, the filter material of the present inventionnot only electro-generates a high quantity of bimolecular Oxygen butusing the direct pass through filtration via the molecular sieve“Zeolite media,” captures the bimolecular oxygen for use for breathingdevices, storage or industrial usage.

The nanocarbon tubular mesh network embedded on the surface of thesynthetic film extends about 0.1 to about 7 millimeters above thesurface of the zeolite coating synthetic film, preferably about 0.2 toabout 6 millimeters and more preferably about 0.2 to about 6millimeters. As with the nanotubles associated with the diRutheniumcontaining carbon-doped film, the nanocarbon tubules can have a diameterof about 20 nanometers to about 450 nanometers. The nanocarbon tubularmesh network can be embedded on the surface of the synthetic film usingany of the following procedures electron-beam lithography, atomic forcemicroscopy, chemically charged molecular ink, crystallizationself-assembly, seeded self-assembly, and mixtures as well as any otherprocedure that does not affect the pores of the synthetic film to whichit is embedded.

One application that can be used in the present invention would be theuse of direct visualization during the embedding process as that by “IBMAlmaden's Materials Characterization and Analysis Lab,” which uses a FEI830 Dual Beam system that integrates the FIB (Focused Ion Beam) with aultra-high-resolution SEM, allowing the analyst to capture an image of aspecific site while performing a milling or deposition procedure. Inmaking the carbon thin film, the thin film is first milled byaccelerated gallium ions so as to dig the initial hole for thenanocarbon tubules to be embedded with the born doped thin film. Oncecompleted, a carbon metal oxide is deposited within the milled region toform a pattern and underside of the carbon tubules while an inert gas,such as Argon, is pumped onto the surface of the thin film. Additionalcarbon doped atoms are deposited onto the argon gas surface above thenanocarbon tubule concavity previously formed in the thin film by thegallium ions. The deposition may be completed either by ALD (atomicLayer Deposition) or CVD so that the carbon tubules are laid down in aconcentric pattern extending from the innermost point of the thin filmoutward. Once carbon nanotubule is completed, the end portion of thecarbon nanotubule is left open so that current can be applied within thecarbon nanotubules. The diRuthenium molecules are then eitheraerosolized onto the prepared surface or applied using CVD so as to bondwith the boron fluorine at the newly prepared thin film surface.

In the alternative, the method used to form the Carbon Boron dopedFluoride film could be by radio frequency magnetron sputtering using acomposite target consisting of h—BN and graphite in an Ar—Fl₂ gasmixture, said mixture formed by photolysis of hydrogen fluoride in asolid argon matrix leading to formation of argon fluorohydride (HArF).Subsequent to the formation, the carbon doped fluoride thin film may becharacterized by X-ray diffraction, Fourier transform infraredspectroscopy and/or X-ray photoelectron spectroscopy. Descriptions ofthese procedures can be found in Preparation of boron carbon nitridethin films by radio frequency magnetron sputtering, Applied SurfaceScience, Volume 252, Issue 12, 15 Apr. 2006, Pages 4185-4189 . . . LihuaLiu, Yuxin Wang, Kecheng Feng, Yingai Li, Weiqing Li, Chunhong Zhao,Yongnian Zhao; and A stable argon compound. Leonid Khriachtchev, MikaPettersson, Nino Runeberg, Jan Lundell & Markku Räsänen. Department ofChemistry, PO Box 55 (A. I. Virtasen aukio 1), FIN-00014 University ofHelsinki, Finland. Nature 406, 874-876 (24 Aug. 2000).

The nanocarbon tubular mesh network of both the boron doped film and thesynthetic film can be arranged in concentric spaced circles startingform the center region of the either the porous boron doped carbon filmor the zeolite synthetic film outwards.

Overall the filter material of the present invention is designed so thatthe zeolite synthetic film screen is placed behind the diruthenium borondoped thin film screen so that the diruthenium screen is proximal to theair flow, i.e., the airflow contacts the diruthenium screen first. Inthis way moisture contained in the airflow is impacted andelectrochemically aided so as to enhance the splitting of water intoHydrogen and Oxygen. The zeolite and diRuthenium screens function intandem. In one preferred embodiment of the present invention, a set ofsix screens can be contained within a cartridge having a frame that canbe used in a patient breathing device. The diRuthenium center and outerborder sandwiching the zeolite center bonded to and surrounded bydiRuthenium walls can be analyzed postproduction by FTIR and or X-raycrystallography for its accuracy and bonded interface.

The cartridge designed so that it can be removed and replaced whenneeded. The cartridge can be made to be recyclable or can be a singleuse device. Many different configurations for the cartridge are possibleand do not limit or change the functionality of the filter material ofthe invention. That is, providing filter material that alternatesbetween a new type of diruthenium/diruthenium boron doped thin filmscreen and a new type of zeolite synthetic film screen that functions intandem to produce bimolecular oxygen to an individual patient forbreathing, to an oxygen storage device or to an industrial consumer. Thepresent inventions unique design simultaneously prevents build up ofradical intermediates during oxygen generation and preventsdecomposition of the oxygen catalysts and anion electrodes used in thefilter material of the present invention.

Specific embodiments of the present invention will be described inconjunction with the attached figures, which are provided to betterdescribe the invention and should not be regarded as limiting thepresent invention in any way.

FIG. 1 is shows a prospective view of the front surface of the porousboron doped carbon film comprising diRuthenium/diRuthenium molecules ofthe filter material of the present invention (10). As stated above andshown in FIG. 1, the mesh-like material in which the screen is made ofis a carbon boron doped screen (15) having a top (55), a bottom (60), aright side (45) and a left side (50). Alternative shapes such ascircular, oval, elliptical, parallelograms in particular, square,rectangular and triangular are also within the scope of the invention.

FIG. 1 shows a rectangular screen for description purposes only butother shapes are envisioned to fall within the scope of the presentinvention. Deposed or embedded in the carbon boron doped screen (15) arenanocarbon tubules (20) that originate from a central point in thescreen and radiate outwards to form a loosely packed coil structure in aconcentric arrangement. Although the nanocarbon tubules areconcentrically arranged, in the alternative, embodiments wherein thenanocarbon nanotubules can be arranged in different patterns dependingon the design and shape of the carbon boron doped screen (15). Thedifferent arrangements of the nanotubules, as with the different shapesof the screen, are also envisioned to fall within the scope of theinvention.

Dispersed throughout the carbon boron doped screen (15) are numerousboron atoms (25). These boron atoms (25) can be evenly dispersedthroughout the screen or may be concentrated within the area of thenanocarbon tubules. Approximately in the center region of the nanocarbonscreen (15) is at least one diRuthenium-substituted polyoxometalate(POM) complex (40). As described above, in one embodiment of the presentinvention the diRuthenium-substituted polyoxometalate (POM) complex (40)comprises a diRuthenium sawhorse molecule (35) attached to a POM (30).The diRuthenium sawhorse molecule (35) is located closet to the screenwhile the POM (30) extends out of the face of the screen. Thisarrangement allows for quick and efficient degradation of water intobimolecular oxygen and hydrogen. This arrangement makes of the firstscreen of a repeating unit of the filter material of the presentinvention.

FIG. 2 shows a prospective view of the back surface of the porous borondoped carbon film (100) comprising diRuthenium/diRuthenium molecules anda siderophore (115). The carbon boron doped screen of the invention hasa top (105), bottom (110), a left side (120) and a right side (125). Thesiderophore (115) is shown in FIG. 2 as being located at the bottom(110) of the screen, however, it is within the scope of the inventionfor the siderophore (115) to be located in other portions of the screendepending on the shape of the screen and the arrangement of thenanotubules. The carbon boron doped screen (15) contains boron atoms(25) as oriented as in FIG. 1 as well as carbon nanotubules (20) and atleast one diRuthenium-substituted polyoxometalate (POM) complex (40) asshown in FIG. 1 and discussed above.

The siderophore (115) can be in the form of a hollow tubular structurehaving a plurality of pores wherein at least one end of the siderophore(115) is in direct communication with at least one end of the nanocarbontubules. In the alternative, the siderophore (115) can be in the form ofan ionically charged plate. Either configuration is designed to capturecharged ions such as, ruthenium ions that may become dislodged from thefilter material so as to protect a patient breathing the oxygen producedby the filter material from inhaling the free ruthenium ions. Either theplate or the hollow tube siderophore (115) can be constructed fromimpregnated polysulfinate resin, ethylenediaminetetraacetic acid (EDTA)and mixtures thereof.

FIG. 3 shows a cross-sectional view of the surface of the synthetic filmcomprising zeolite crystalline bodies of the present invention (200).This is the next screen in the repeating unit of the filter and ispositioned facing the back surface of the boron doped carbon film havingthe siderophore shown in FIG. 2. The synthetic film (200) has a top(205), a bottom (210), a right (220) and a left (225) side and is shownin a rectangular configuration. As with the first screen, the syntheticscreen is shown in a rectangular shape but alternative shapes such ascircular, oval, elliptical, parallelograms in particular, square,rectangular and triangular are envisioned to fall within the scope ofthe invention. That is, FIG. 3 shows a rectangular screen fordescription purposes only but other shapes fall within the scope of thepresent invention.

As with the boron doped carbon film of FIGS. 1 and 2, the synthetic filmhas carbon nanotubles embedded or deposed thereon. The synthetic screenalso has zeolite crystalline bodies (240) in direct contact with thenanotubules (215), the synthetic film or both.

FIG. 4 shows a cross sectional view of a plurality of alternatingscreens of the filter material of the present invention (300). Thealternating stacked arrangement comprises a first boron doped carbonfilm comprising diRuthenium/diRuthenium molecules and at least onesiderophore (305). The second screen in the filter material of thepresent invention is the zeolite containing synthetic film (310) whichis followed by another boron doped carbon screen (315) and then anotherzeolite containing synthetic film (320). This repeating alternatingstacking of the two types of screens can be repeated until the desirednumber of screens is reached. The screens can each have a frame that canbe encased in a cartridge or in the alternative the screens can beframeless and encased in a cartridge as frameless. The cartridge assuresthe integrity of the filter material made from the alternating repeatingscreens.

FIG. 5 shows a prospective view of a plurality of alternating screens ofthe filter material of the present invention in a filter cartridge(400). This cartridge (400) can have many different shapes and sizes andcan be used in a oxygen producing machine for breathing or in thealternative an oxygen producing device used for industrial purposes asdescribed above.

While the above description contains many specifics, these specificsshould not be construed as limitations of the invention, but merely asexemplifications of preferred embodiments thereof. Those skilled in theart will envision many other embodiments within the scope and spirit ofthe invention as defined by the claims appended hereto.

1. A filter material for generating/removing oxygen and/or hydrogen gasfrom a source comprising: a porous boron doped carbon film comprisingdiRuthenium/diRuthenium molecules and at least one type ofelectronegative ion, said diRuthenium/diRuthenium molecules and saidelectronegative ion are positioned in direct contact with said porousboron doped carbon film whereby oxygen and/or hydrogen gas is generatedfrom a source as it passes across said filter material.
 2. The filtermaterial of claim 1 wherein said diRuthenium/diRuthenium molecules indirect contact with said porous boron doped carbon film is ionicallybonded.
 3. The filter material of claim 1 wherein said porous borondoped carbon film further comprises a nanocarbon tubular mesh network.4. The filter material of claim 1 wherein one diRuthenium molecule ofeach of said diRuthenium/diRuthenium molecules has the following formula(I)[Ru₂(CO)₄(u-n²⁻O₂CR)₂L₂]_(x)   (I) wherein u is a bridging ligandselected from the group consisting of [Ru₂(EDTA)₂]²⁻, (CO)₄, F⁻, Co₃ ⁻²,NO⁺ (Cationic), Hydrogen-bonded aromatic/carboxylic Acid-(either formultiple attachments as polymerization or singular, at the double bondedOxygen or sites within), ethylenediamine, halides as anionic ligands,carboxylic acid, unsaturated hydrocarbons, Nitric Acid coordinating to ametal center either linear or bent, butadiene, carboxylate ligands,anionic (RO— and RCO₂ ⁻² (wherein R is H or hydrocarbon) or neutralligands (R₂, R₂S, CO, CN⁻), CH₃CN (Acetonitrile), NH₃ (Ammonia ammine)F⁻, Cl⁻, tris(pyrazolyl)borates and mixtures thereof, preferably[Ru₂(EDTA)₂]²⁻; wherein n is at least 2 and depends on the denticity ofthe molecule—(that is, the number of donor groups from a given ligandattached to the same central atom); wherein L is a ligand selected fromthe group consisting of [Ru₂(Ph₂PCH₂CH₂PPh₂)(EDTA)]²⁺, C₆H₆R₂C=CR₂(wherein R is H or an alkyl), 1,1-Bisdiphenylphosphino methane,diethylenetriamine [diene] bonds preferably tridentate,triazacyclononane [diene] bonds preferably tridentate,triphenylphosphine and mixtures thereof; wherein CR is carboxylic acid,carboxylate ligands, anionic (RO— and RCO₂ ⁻(wherein R is an alkylgroup)) or neutral ligands (R₂,R₂S, CO⁻, CN⁻ (wherein R is an alkylgroup)) and mixtures thereof; ; and x is between 1 and about
 30. 5. Thefilter material of claim 4 wherein one diRuthenium of saiddiRuthenium/diRuthenium molecules of formula (I) is attached to adiRuthenium-substituted polyoxometalate having the following formula(II)[WZnRu^(III) ₂ (OH)(H₂O)(ZnW₉O₃₄)₂]⁻¹⁴   (II).
 6. The filter material ofclaim 5 further comprising a Ruthenium ion capturing siderophore plateconnected to the opposite surface of said porous boron doped carbon filmin which said at least one diRuthenium/diRuthenium molecule is attached,said siderophore plate ionically charged so as capture free Rutheniumions that become dislodged from said porous boron doped carbon film. 7.The filter material of claim 6 wherein said siderophore plate isselected from the group consisting of a polysulfinate resin impregnatedplate, ethylenediaminetetraacetic acid (EDTA) and mixtures thereof. 8.The filter material of claim 5 wherein the distance between eachRuthenium in said diRuthenium molecule is about 2.75 angstroms.
 9. Thefilter material of claim 8 wherein said nanotubles of said nanocarbontubular mesh network have a diameter of about 20 nanometers to about 450nanometers.
 10. The filter material of claim 4 wherein x is between 1and about
 10. 11. The filter material of claim 5 further comprising asynthetic film comprising a plurality of nanocarbon tubules attachedand/or embedded on a surface of said synthetic film to form a nanocarbontubule mesh network, said synthetic film positioned in closecommunication with said surface of said porous boron doped carbon filmcomprising said siderophore.
 12. The filter material of claim 11 furthercomprising at least one zeolite crystalline body in direct contact withsaid nanocarbon tubules wherein said synthetic film comprises amultiplicity of pores having a diameter of about 0.1 about 3.0 nmwherein said zeolite crystalline attached to said nanocarbon tubulesoverlap at least part of said pores to form a repeating unit of saidfilter material for removing oxygen and/or hydrogen gas from a source.13. The filter material of claim 11 wherein said synthetic film is SiO₄,AlO₄, and mixtures thereof.
 14. The filter material of claim 11 whereinsaid nanocarbon tubular mesh network embedded on said surface of saidsynthetic film extends about 0.2 to about 5 millimeters above saidsurface.
 15. The filter material of claim 12 wherein said nanocarbontubules of said nanocarbon tubular mesh network have a diameter of about20 nanometers to about 450 nanometers.
 16. The filter material of claim12 wherein said nanocarbon tubular mesh network is embedded on saidsurface of said synthetic film using electron-beam lithography, atomicforce microscopy, chemically charged molecular ink, crystallizationself-assembly, seeded self-assembly, and mixtures thereof.
 17. Thefilter material of claim 2 wherein said nanocarbon tubular mesh networkis arranged in concentric spaced circles starting form a center regionof said porous boron doped carbon film outwards.
 18. The filter materialof claim 11 wherein nanocarbon tubules embedded on said surface of saidzeolite containing synthetic film is arranged in concentric spacedcircles starting form a center region of said porous boron doped carbonfilm outwards.
 19. The filter material of claim 5 wherein saiddiRuthenium-substituted polyoxometalate of formula (II) isNa₁₄[Ru₂Zn₂(H20)₂(ZnW₉O₃₄)₂].
 20. The filter material of claim 12wherein said diRuthenium-substituted polyoxometalate of formula (II) isNa₁₄[Ru₂Zn₂(H20)₂(ZnW₉O₃₄)₂].
 21. A method for producing oxygen and/orhydrogen comprising providing a flow of air containing water across thefilter material of claim 12 to produce oxygen and/or hydrogen from saidfilter material.